Vanadic acid esters of homocyclic alcohols



invention rrelates'v'fto estersrr l r,cyclic alcoholsand vanadic acids. 1

' 4Vanadium compoundssuch asvaadiurn pent'-y mmo- 5 tion catalysts/in l a great many .reactionsl forex- 1 ampleconverting sulfur dioxide to trioxide, sugar to oxalic acid, naphthalene .to iphthalicanioxideLfIn this type off reactio'nfit.r is important '.fthat the temperature Ibecontrolled withina cercompletecombustion v takes placeyto an increas- ,i'lower'.,v vMany of these disadvantages are avoided -der ywhich these Afoxidations yare carried; out` in 'fdium compounds generallyv lai'gailzible 'heretofore l25` oxidationreactions.

pr`oduce'd-whichl have (unusual properties of con-1 f siciereblecommercial'infiport'ancez They arey generally soluble inl organicliquids and-particularly.

'g f `canfbefused tol improve the burning-character-V 'istics'of fuel oil. v

; is in the oxidizing otorganic compounds in the extremey opacity vto ultra violet light and are yuseful las light screens vin-'various lacquers or ,resinouscompositionsto block out undesirablev incorporatedy into'4 nitrocellulose rand cellulose acetate s'heetmaterials to exclude harmful light rays. Certain ofthe vanadic esters ofthe pres'- ent invention havebeen found to beus'eful in f i 'solubility properties of these esters make themv f particularly useful as dri'ers and` they produce a v ,f rapid and uniform oxidation of paint andvar- 504V nish'coatings. v f f v It'isnot necessary lthat the vvanadicvesters of v the present inventiongbe in a pure formto be 1 useful inthe variousoperations as pointed outv i above; Catalytic ,action and opacity to `ultravio fx-letlight is due vanadium itself.` v The composioxide have been usedextensively'as-solid oxidaj hydride; anthracene to ganthraquinone. Many oftheabove reactions are carried out in thevapor 0` phase 'inwhichja gaseous 'fmixture ofthe reactv f' f ing substances is passed overthe Vanadium pent-V gtain range. *If' theftem'perature rises too high ing: extentand the ffyields are correspondinglyy by liquid phase'oxidatioris.- The conditions un'- rvgeneraliaremore easily controlled thantheJ-vapor v vphase oxidation reaction. 1-Iowev'er,' the vana--v have not'gbeen 'soluble inorganic liquidsfand (hence could not bezusedeffectively in liquidfphase`- f y f 1"'I echn1cal 85%-V2O5j-was-boiledgently'withggg z According to the present inventionv various' .bellZyl '310.01101 fQraboutitWO- hoursrand thenl- .vanadicacid1'esters'of/nonocyclic' alcoholsfareg 4 A Y p Y was avery .dark gray-witha violettlntfqfjThesoe kShekine with -Watcll' yellow C'Qlorationwaslpro- 30 ypetroleum products `such 'as fueloil'fandfhenc'e' *Y nbeen' formed. The y1eldy is not VquantitatiVel?as *,Anothe'r seid for thelurseof thesefcoinp'oums gaseousand especially liquid'phas'e oxidation4 yagprocedures.A These vanadic esters alsc e'xhibit'A for about` three' hours. v The solution 4was very ywater a yellow colorationjwas produced indifv 4b" short light Wavev radiations. They mayalso be paints and'yarnishes as driers. rThe improved addition of water'a yellow coloration was proT f ducedv which indicated that tetrahydrofurfurylm 1 that cyclic alcohols will react dlrectlyfwith V205 Vtions ofthepresent invention therefore,`j.may

- eithery the orthoyanaldicester of 'a1 cyclic alcoh l Y f the nietav'anadic' ester .of a cyclic alcoholI or'ot e p olyvanldic esters o r mixtures and VVso utions los. .the VI-S, esters r v @f6 the' present'invention 'l fi Y y f Y. 'Example' ",:Technical85%'V2O5`wasintroduce nto c lolo h exanol and the mixture was'. boiledgentlylfor f' 1 about two hours. lThe solution assumeda yellow Y color'whch deepenedto a reddishbrownas *ther boiling progressed.' The solutionw'as filtered to"l remove the excess V205 and yielded-a`reddish15 brown 'solution which was foundj tofbefmiscible With kerosene and k ay heavyjliquid petroleum. Water was addedto'a portion of the yiilterfeds olu v 'tion f whereupon the water was'icolored"yellowj j An analysis showedfavvanadium pentoxidefcon- 2 tent of 7.38% which corresponds to an ester conlution was `found lto l'bey solubleif kerosene. ;Upon

duced showing that' theibenz'yi:vanadtehad -tion of b en'zaldehyde...

ysome decomposition takes place with'thecform'a? 1 f Example i3 Technica-i1 85%'v2o5`was boiled withv terpineoi' darkwith av brownish tint. Upon the'addit'ion of eating 1 that terpineol vanadate hadfbeen' produced; The'product can jbe dissolved in kerosene;vv

toluenel anda heavy petroleum oil. j

ExampleV v4 Y l, .45 ',Iechnicaljv 85% V205. was boiled withatetra'` L hydrofurfury1 alcohol'and -1tered. The solution was verydarkwitha'greenishftint. Upon/ tliejI vanadatehad been produced. The solutionw'as found to be miscible with` kerosene and a heavy` f petroleum oil.` f

While it is apparent from the above,` examples to form vanadates by simply boiling the components, other methods may also be used in some cases, such as making a vanadate of an alcohol of a suitably low boiling point and then replacing that alcohol by one of higher boiling point. This method is particularly advantageous where the vanadates of the higher boiling point alcohols decompose readily at the boiling point of the alcohol of Where the alcohols are easily oxidized. Reactions between the higher boiling alcohols and V205 may also be carried out advantageously in the presence of a lower boiling inertA solvent. In some instances the liquid in `which the ester is to be used as a catalyst can serve as the reaction medium.

The esters of the present invention are usually produced in the form of a mixture of esters of ortho, meta, and higher polyvanadic acids. The proportions of the particular esters will vary with temperature, light, presence of moisture and the like. In general, high temperatures and anhydrous conditions favor the ortho, Whereas lower temperatures and the presence of moisture result in a larger proportion of the meta and `higher polyvanadates. Except for Vthe fact that .the polyvanadic esters are colored, Whereas the ortho esters are light colored or colorless, the esters are substantially equivalent for most commercial uses, and the exact composition of a particular CERTIFICATE OF CORRECTION Patent No. 2,220,0ll1.

It is hereby certified'that errorapp ofthe above numbered patent requiring c column, line 27, for

ord of the case in the Patent Office.

Signed and sealed this 5rd day of December,

(Seal) lcyclic alcohols,

ears in orrection as follows; Page 1, first "monocyclic" read -homocyclic; page 2, first coland that the ,said Letters Patent" Should mixture is not usually ofimportance. Where it is desirable to separate the esters, this can be simply effected by suitable fractional distillation, preferably under vacuum. Another method of isolating the individual esters is bycooling and concentration. These procedures materially increase the cost of the product and for most uses the isolated estersv do not produce any advantage.

While the foregoing examples relate to the production of the vanadic esters of representative the present invention is not limited thereto, but includes broadly the vanadic esters of any esteriable cyclic alcohol belonging to the carbooyclic or heterocyclic series. Among thel other alcohols which may be used to produce the esters of the present invention are methylcyclohexanol, dimethylcyclohexanol, the menthols, tolyl alcohol and phenylethyl alcohol.

What I claim is:

1. An ester of a homo cyclic alcohol and Vanadic acid.

2. An ester of an aromatic alcohol and vanadic acid.

3. An ester of an alicyclic alcoholand vanadlc acid.

4. A cyclohexyl vanadate.

5. A benzyl vanadate.

october 294, i9llo.

WILLIAM H HILL the printed 'specification seme may conform to the rec- A. D. 191m.

Henry Van Arsdale, ActingA Commissioner of Patents.

. H. HILL.

CERTIFICATE OF CORRECTION. v l Patent No. 2,220,0191. october 29, 19m).

- WILLIAM H. HILL.

It is hereby certified that error .appears in the printed specification of the above numbered patent requiring correction as follows: Page l, first column, line 27,v for "monocyclic read -homocyolic; page 2, first column, line 9, for r"of" read -or; :and that the said Letters Patent-"should be read with this correction therein that the same may confom to the record of the case in the Patent Office.

signed and sealed this 5rd dey of December, A. D. 19m.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

